Unlted States Patent [19]

McGrew et al.
[54] IODINE LEACH FOR THE DISSOLUTION
OF GOLD -

[11] Patent Number:

[45] Date of Patent:
2/1980 Bah] et a1. . . . . . .

4,557,759
Dec. 10, 1985
. . . .. 156/664

4,131,454 12/1978 Piret et al. ...................... .. 75/ 118 R

4,190,489

4,319,923

3/1982

Falanga et a]. .

..... .. 75/108

[75]

Inventors: Kent J. McGrew; Jack W. Murphy,

4,375,984 3/1983 Bahl et al. ........................ .. 75/97 A

both of Laram'e, W o. l y

Primary Examiner-John Doll

[73] [21] [22] [51]

Assigneei In-Situ, Inc., Laramie, WyOAppL No: 598,706 Filed: Apr. 10, 1984 Int. cu ............................................ .. C22B 11/04
204/111 Field of Search ........... .. 204/111; 75/118 R, 108,

Assistant Examiner-Robert L. Stoll Attorney, Agent, or FirmSheridan, Ross & McIntosh [57] ABSTRACT A Process for the hvdrometallurgical recovery of gold
from {mammals contelmng gold comprlsmg leachmg the materlals with a lixlviant containing iodine. To a solu
tion concentrated with natural salts is added elemental iodine until saturated, whereupon mineral sul?des in the

[52] US. Cl. ............................. .. 75/118 R; 75/101 R; 75/108; 423/38; 423/39; 423/42; 423/46;
[58]

75/ 121, 101 R; 423/38, 42, 39, 46; 156/654, 187 R; 252/79 R
.

ore zone charged with this solution react with the io dine to form iodide. Additional elemental iodine is then
added to this iodide-bearing solution until the desired

[56]

References cued U-S- PATENT DOCUMENTS 2,304,823 12/1942 3,495,976 2/1970 $625,574 4/1969

concentration of total iodine and ratio of iodine to io= dide are achieved for optimum leaching. The lixiviant is then circulated through the ore zone until all the gold is dissolved. Gold is subsequently recovered on activated charcoal. The excess iodide formed during the process is reoxidized to iodine electrochemically in a special

3826750 7/1974
3,957,505 5/1976
3,957,603 5/1976 Rhodes .............................. .. 204/ 111

diaphragm cell to regenerate the lixiviant.

14 Claims, 2 Drawing Figures

CRUDE IODINE (I2)

I2 SOLUTION-151' CYCLE

I SOLUTION- 1ST CYCLE

"

eREcovtRY
WELL

INJECTION-I
WELL

PUMPJH

SOLUTlON FLOW
THROUGH ORE BODY

U.S. Patent De'c. 10,1985

Sheet10f2' 4,557,759

FIGURE 1
CRUDE IODJNE (IL)

IV I: SOLUTION-1ST CYCLE LI- soLLmoN- 1ST CYCLE L

P-REcovERY
WELL

LNJEcnoNf
WELL

ORE ZONE REACTION?

F632 + 712. + 8H2O+F E*2+25OI+1+|6H ++ |4I _ FeSz+I2+HzO- FE+2+ 25 +21

PUMPJ]

OLUTION FLOW4
THROUGH ORE BODY J

U.S. Patent Dec. 10,1985

Sheet2of2

4,557,759

FIGURE 2

D. C. POWER SUPPLY

IIIIIIF
. DIAPHR/IXM CELL

GOLD

BANODE
("9 i
i 7

CATHODE
9

K'L g]

0/ Na CI

Rgg/gvfifiv
u a

bid NaCI/NaOH WASTE

.
lREcovERv

SOLUTION

17E; I_\XIVIANL
LNJECTIONY '

WELL

WELL

ORE ZONE REACTION

DISSOLVES GOLD

ANODE- REACTIONI 311-9115 + 26'

CATHODE REACTIONI Ze-+ZHZO>HZ+ZOH NET REACTIONI ZHZO+3I__' leT+Hz+ZOH'

1
GOLD

4,557,759
mitigated.

2
DESCRIPTION OF THE DRAWING

exhaustion and consumption of scarce iodine are greatly

IODINE LEACH FOR THE DISSOLUTION OF

TECHNICAL FIELD

This invention lies in the ?eld of hydrometallurgy. In

FIG. 1 is a ?owchart showing a preferred embodi ment of the process of this invention.

particular, it involves the recovery of gold by in-situ, heap leach, and agitated leach processes.
BACKGROUND OF THE INVENTION In most hydrometallurgical processes for the recov ery of gold, elemental gold is solubilized by oxidation to

FIG. 2 depicts a diaphragm cell for oxidation of io dine.

SUMMARY OF THE INVENTION

Gold is recovered from gold bearing materials, par

ticularly gold ores, by oxidation with iodine and com plexation with iodide in an aqueous, electrically con
ductive lixiviant. The oxidation of sul?de minerals or other iodine reducing species in the ore zone contacted

ionic gold and complexation with cyanide. While the

use of cyanide for gold recovery systems has been the primary process for the recovery of gold for many

problems.

decades, the toxicity of cyanide makes introduction into groundwaters associated with gold ores highly undesir able. Apart from the toxicity of cyanide to man, its use poses long-term environmental and waste disposal 20
Consequently, the use of iodide as a complexing agent

by the iodine-bearing lixiviant yields iodide as a reaction product. On subsequent addition of more iodine to the

lixiviant, iodine is complexed by iodide and is dissolved

until the desired concentration of iodine is achieved. Thus no alkali cations need be added to the lixiviant. To maintain the desired ratio of iodide to iodine complex (tri-iodide), the lixiviant is subjected to an oxidation process. In a preferred embodiment, the lixiviant is

in the gold recovery process carries with it signi?cant

bene?ts. Direct bene?ts are derived from the lack of immediate pollution of the leach area with a highly 25 passed through a special diaphragm cell where iodide is electrochemically re-oxidized to form the iodine com toxic material, such as cyanide. In addition, the reduced

requirements of containment and disposal of leach

waste materials are highly economic. This is particu larly true of in-situ leach processes where such factors are of great concern in determining the economic feasi

plex. Preferably, this method relies on the presence of

common groundwater salts (e.g., NaCl, NaHCO3, Nag. S04, etc.) to render the lixiviant electrically conductive
as it passes through the diaphragm cell. Gold recovery from the withdrawn lixiviant is preferably by means, such as activated charcoal, which do not affect the

bility of gold recovery.

While iodine leach processes are well known in the

art, a signi?cant problem with prior methods is that they suffer from inef?cient recovery and reuse of io
dine. Much of the iodine is consumed by the ore body. Since iodine is only 300 times more abundant than gold itself, this relative scarcity can make the use of iodine

iodine rich lixiviants ability to oxidize, complex, and dissolve the gold. Gold recovery is also possible by loading on suitable resins, cementation, and the like.
The use of iodine in the lixiviant obviates the need to use toxic materials such as cyanide in the gold leach

too expensive for commercially economic recovery of

gold via in-situ leaching processes.

Another problem with these processes concerns the solubility of iodine in a typical aqueous system. Alkali metal cations, such as sodium and potassium, generally
must be added to promote dissolution. This addition of

process. Gold oxidation, complexation and dissolution are rapid, and effective recovery of the gold at accept able leach rates is possible. The use of electrochemical oxidation for regenera tion of iodine complex from iodide in solution obviates the need for reintroduction of signi?cant additional

amounts of scarce elemental iodine. foreign cations generates a substantial portion of the 45 The process of this invention herein described can be cost associated with waste handling and restoration of used for in-situ leaching, or for heap, or agitated leach the mining area, and is therefore undesirable.

Finally, while some gold recovery methods allowing

the use of iodine employ reoxidation of the iodine in
order to conserve the iodine for reuse, these methods

ing with additional modi?cations.

DESCRIPTION OF THE PREFERRED EMBODIMENT

typically require the introduction of oxidizing anions

such as chlorine. This is also undesirable for both the ecological and economic reasons discussed above with respect to the addition of cations. The inventors process overcomes these problems with prior known methods. The instant process com

The solubilization and recovery of gold requires that

the gold be oxidized from its native or elemental form to an ionic state. All of the halogen group of elements, i.e.

?uorine, chlorine, bromine, and iodine, readily oxidize

gold. Once oxidized, ionic gold is stabilized in solution (solubilized) by complexation with a complexation agent. Chlorine, bromine, and iodine form stable Au(I) or Au(III) complexes in aqueous solutions with the respective reduced species of the element (e.g.,

prises a practical mining technique for the recovery of gold from permeable gold ores which does not require

the introduction or use of toxic species such as cyanide. Moreover, the method allows the use of iodine in the 60 AuCl2, AuCl4). Gold dissolution may occur in an leach process without the addition of cations into the aqueous iodine/iodide system according to the follow lixiviant in order to promote dissolution of iodine dur

ing its introduction into the leach. Finally, the process

permits reoxidation of the iodide to iodine, thus con

ing equations:

serving the starting material, without the introduction

of oxidizing anions, such as those of chlorine, chlorate,
or hypochlorite. Thus the costs associated with envi ronmental clean up of toxic materials, and with the

65

4,557,759

Neither equation 1 or 2 is favorable at standard poten

in solution. On completion of gold recovery, the lixivi

ant may be advanced to the next zone to be mined.

tials. However, standard conditions rarely prevail in real systems. Moreover, for a given weight/volume
concentration of total iodine (where total iodine is

Since reduction of the Ig-complex continues as in

equations 1 and 2 during the oxidation and complex

iodine to oxidizing iodine in the lixiviant. In the pre ferred embodiment, the re-oxidation of I-is accom

de?ned as all species of iodine in solution, e. g. I, I2.I, 5 ation of the gold, some means of re-oxidizing the Iis necessary in order to preserve the 2:1 ratio of reduced 1;, etc.), by varying the distribution of iodide, tri-iodide,

and iodine, it is possible to bring about a net spontane ous reaction for the oxidation and complexation of gold. In the preferred embodiment of the process, elemen
tal iodine is added to a solution to form a gold lixiviant

plished electrochemically in the anode compartment of

a special diaphragm cell, as illustrated in FIG. 2. Oxida tion of iodide is achieved by the half cell reaction:
3I->I3-+2e. (6)

or leach. The solubility of the iodine will be limited

initially to about 0.3 g/l (elemental 1;). However, gener

ally a higher total iodine concentration is desirable for economic application of the process. The process may
be conducted with a concentration of total iodine on the

15 Reduction of water occurs at the cathode according to

order of between about 0.3 g/l and the upper solubility limit of total iodine in the system, preferably between about 1 and about 20 g/l, more preferably between about 2 g/l and about 5 g/l, and most preferably about 20 The net cell reaction, the sum of reactions 6 and 7, is:

the half cell reaction:

3 g/l.

It is possible to achieve this higher concentration of

iodine (1;) by reacting it in solution with sul?de miner

als in the ore body, such as marcasite (FeSZ), chalcopy

rite, chalcocite, covellite, galena, pyrite, and the like, to create iodide (I') by the following reactions:

25

The diaphragm itself comprises a porous membrane separating the anode and cathode compartments of the
cell. The half cells are in electrical contact, but the

diaphragm prevents signi?cant mixing of the lixiviant at

the anode with the cathode solution. The means by which an appropriate cathode solution can be prepared 30 are well known to the art, as is the general construction
of the entire electrochemical cell. -

FeS2+I2-+Fe+2+2S+2I-

(4)

To ensure suf?cient iodide formation, the ore body being mined must contain some sul?de minerals, or

In a preferred embodiment salts from the mining aquifer are used to effect the desired electrical conduc
35

other iodine-reducing species. However, the absence of

, <such minerals or species is extremely rare. The presence

tivity of the anode (lixiviant) and cathode solutions. Generally, the aquifer will contain suf?cient groundwa
ter salts, such as NaCl, NaHCO3, and Na2SO4 so that solutions can be prepared with ?nal salt concentrations

of between about 5 g/l and about 20 g/l, preferably between about 8 g/l and about 12 g/l, and more prefera am through the ore zone, returning it to the surface, and bly about 10 g/l. Such concentrations are easy to obtain -~.:-v subsequently adding more iodine, iodine is dissolved by via reverse osmosis of intrinsic groundwater having a theformation of the tri-iodide complex (121- or 13-) salt concentration of 0.5 g/l or higher. In addition other according to the reaction: techniques well known to the art, such as electrodialy sis, or ion exchange, can be used to accomplish the 45 I2+II2.I" (5) concentration of these salts. The process of this invention is further illustrated as It is possible by repetition of this step, which is illus follows: trated in FIG. 1, to approximately double the total ILLUSTRATION iodine concentration of the lixiviant with each iodine addition until the desired concentration, preferably PHASE ITotal Iodine Build-up about 3.0 g/l has been achieved. The ratio of reduced Gold ore containing marcasite is loaded into transpar iodine (I-) to oxidized iodine (1;) on a weight basis ent columns connected in series to form a total length of in the lixiviant is limited only by the solubility of such about 120 feet, corresponding to one pore volume, in

,-of I-(reduced iodine) in the spent lixiviant greatly increases the solubility of I; (oxidized iodine) subse y-zquently added to the lixiviant. By circulating the lixivi

species in the solution, but is preferably between about 55 order to simulate an ore body for in-situ leaching. Dur 10 to l and about 1 to 10, and more preferably about 2 ing Phase I of the experiment, the total iodine concen to l (i.e. 2 g/l I-: 1 g/l 1;). For economic reasons, this tration of the lixiviant is doubled with the cycle of each ratio of 2 to 1 is very desirable, but practice of the in pore volume of column eluent through the simulated

ventors process is obviously not limited to this speci?c ore body. Initially, iodine is added to the lixiviant in a ratio. 60 concentration of about 0.3 g/l (Imml Table 1). Prior to Once the iodine concentration has been raised to the the introduction of this lixiviant into the columns (pore desired level, the lixiviant is circulated through the ore volume 0, Table 1), all of the iodine exists in solution as body as many times as necessary to effect complete oxidized iodine (Ioxid Table 1). This is because none of recovery of the gold. The actual recovery of gold from the iodine is reduced until it contacts iodine reducing the lixiviant, once withdrawn, can be carried out by 65 species within the ore body, such as mineral sul?des. means such as activated charcoal, or by other means After the lixiviant is passed through the ore body once previously mentioned or known to the art, without (pore volume 1, Table l), 0.3 g/l additional iodine is' requiring any further addition or treatment of the iodine injected into and dissolved in the lixiviant (giving a total

4,557,759

6
solved by reaction With iodine, all in the substantial
absence of added cations to promote dissolution of the iodine in order to oxidize elemental gold to

iodine concentration of 0.6 g/l); however, since all of the iodine previously injected has been reduced (Ired Table 1), only 0.3 g/l of the iodine added to this ?rst pore volume is present as oxidized iodine. This cyclic addition and dissolution of iodine is repeated through out Phase I of the experiment, until four pore volumes

ionic gold, and to complex the ionic gold, thus

have been passed through the columns.

It should be noted that no gold is recovered during Phase I of the experiment. This is because during Phase
I an insufficient excess of oxidized iodine is present in

maintaining the gold in solution; and (b) recovering the gold from the pregnant lixiviant.
2. The process of claim 1. in which the gold-contain ing material is leached in-situ.
3. The process of claim 1 in which the iodine dissolu tion process is repeated until the total concentration of iodine in the lixiviant is between 1 and about 20 gram/ liter. 4. The process of claim 1 in which the iodine-reduc ing material is a mineral sul?de. 5. The process of claim 4 in which the iodine-reduc

the lixiviant, and all of the oxidized iodine is consumed before the lixiviant reaches the end of the columns.

Consequently, any dissolved gold precipitates before

emerging with the lixiviant. However, once the entire pore volume of the ore body contains a slight excess of oxidized iodine, the dissolved gold present in the lixivi ant remains in solution, and is eluted from the ?nal column. TABLE 1
Recov

ing species comprises marcasite.

6. The process of claim 1 in which the gold-contain
20

ing material is leached by a heap leach process. 7. The process of claim 1 in which the gold-contaim ing materials are leached by an agitated leach process.
8. The process of claim 2 in which a desirable concen

Pore

Injected

Injected

ered

% Au

Volumes
0 l 2 3 4

1m! (M)
0.3 0.6 1.2 2.0 3.0

Iuxid (g/I)
0.3 0.3 0.6 0.8 1.0

Imi (all)
0.0 0.3 0.6 1.2 2.0

recovered

tration of oxidized iodine in the lixiviant is maintained by reoxidizing excess iodide in the spent lixiviant elec
25

trochemically using an electrochemical cell utilizing concentrated ground water salts from the mining aqui
fer to provide oxidizing anions for the process. 9. The process of claim 8 in which the electrochemi cal cell is comprised of an anode half cell through which the spent lixiviant is passed], and a cathode half cell through which conductive water is passed, and wherein said half cells are separated by a diaphragm
comprised of a porous membrane which does not allow

EXAMPLE PHASE IIGold Recovery

To the transparent columns described in the above Illustration, was added a lixiviant containing 3.0 g/l

signi?cant mixing of the anode and cathode solutions.

10. The process of claim 1 in which the means of recovering the gold from the pregnant lixiviant com prises contacting the lixiviant with activated charcoal. 11. In a process for maintaining the presence of gold oxidizing iodine in a lixiviant solution comprising:

total iodine. Once the gold had started to elute, the

recirculation of ?ve additional pore volumes resulted in 95% recovery of the gold recoverable by this process

(% Au recovered, Table 2). Gold recovered in the

process was 80% of total gold present in the ore. It should be noted that is was necessary to inject fresh iodine into the lixiviant to replace iodine recovered as

(a) dissolving elemental iodine in the lixiviant;

(b) reoxidizing reduced iodine in the lixiviant to oxi dizing iodine by means of electrochemical oxida

reduced iodine after each pore volume passed through

the ore body.
TABLE 2
Recov
Pore Injected Injected ered % Au

tion, the improvement comprising conducting the oxida

tion in an electrochemical cell comprised of an
45

anode half cell through which the lixiviant-bearing

reduced iodine is passed, a cathode half cell through which conductive water is passed, and a porous membrane which allows electrical contact

Volumes
l 2 3 4 5 6

Inna] (g/l)
3.0 3.0 3.0 3.0 3.0 3.0

Ion-,1 (gm
1.0 1.0 1.0 1.0 1.0 1.0

1,8,1 (g/l)
2.5 2.5 2.5 2.5 2.5 2.5

recovered
30 60 75 84 90 95

What is claimed is: 1. A process for the recovery of gold from a material

between the half cell solutions but prevents signi? cant mixing of said solutions, in which the cathode solution is obtained from the mining aquifer and where the electrical conductivity of said solution is increased by means of concentration of ground water salts naturally occurring in said aquifer.
12. The process of claim 11 in which the reduced iodine is formed during in-situ leaching of an ore body. 13. The process of claim 11 in which the lixiviant anode solution is initially obtained from the mining area

containing gold comprising:

(a) contacting the material with a lixiviant comprising
a solution in which elemental iodine has been dis

solved by means of adding iodine to the lixiviant, passing the lixiviant through ore bearing an iodine reducing material, allowing the iodine to react with

aquifer and where the electrical conductivity of said

solution is increased by means of concentration of

groundwater salts naturally occurring in said aquifer.

14. The process of claim 11 where gold is recovered from the lixiviant prior to reoxidat'ion of the iodine.
* * * * *

said iodine-reducing material to produce iodine,

and subsequently adding more elemental iodine to this same lixiviant whereupon more iodine is dis
65